CA2423206C - Halogenated elastomeric compositions having improved stability and green strength - Google Patents
Halogenated elastomeric compositions having improved stability and green strength Download PDFInfo
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
- C08L23/28—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by reaction with halogens or compounds containing halogen
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- C08L23/28—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by reaction with halogens or compounds containing halogen
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- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
- C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
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- C08L21/00—Compositions of unspecified rubbers
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- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
- C08L23/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
- C08L23/22—Copolymers of isobutene; Butyl rubber ; Homo- or copolymers of other iso-olefins
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- C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
- C08F2800/20—Copolymer characterised by the proportions of the comonomers expressed as weight or mass percentages
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- C08F2810/00—Chemical modification of a polymer
- C08F2810/50—Chemical modification of a polymer wherein the polymer is a copolymer and the modification is taking place only on one or more of the monomers present in minority
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- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
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- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
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Abstract
The present invention is a composition and a method of forming a composition, the composition comprising at least a halogenated elastomer and an amine or phosphine. An additional rubber component may be present in the composition of the invention. Ine one embodiment, the halogenated elastomer is a isoolefin copolymer comprising a halomethylstyrene derived unit. The amine or phosphine compound is represented by the formula (R1R2R3)Q, wherein Q is a Group 15 element, and wherein R1 is either hydrogen or a C4 to C30 hydrocarbyl group, R2 is either hydrogen or a C1 to C30 hydrocarbyl group; and R3 is either hydrogren or a C1 to C30 hydrocarbyl group provided that at least one of R1, R2 and R3 is not hydrogen. The additional rubber is selected from butyl rubber, halogenated butyl rubbe, star-branched butyl rubber, halogenated star-branched butyl rubber, isobutylene homopolymer, butadiene rubber, neoprene, nitrile rubber, ethylene/propylene/diene terpolymers, ethylene/propylene copolymers, styrene butadiene rubbers, polybutadiene, polyisoprene, isoolefin/alkylstyrene copolymer, halogenated isoolefin/alkylstyrene copolymer, natural rubber, polypropylene, polyethylene, polyurethane, polyvinyl chloride, silicon rubber, propylene oxide polymer, and mixtures thereof.
Description
TITLE: HALOGENATED ELASTOMERIC COMPOSITIONS
HAVING IMPROVED STABILITY AND GREEN
STRENGTH
FIELD
The present invention relates generally to elastomeric compositions having improved thermal stability and green strength. These elastomeric compositions include compositions of a halogenated elastomer such as an isoolefin copolymer comprising a halomethylstyrene derived unit, and an am'ine. The composition may also include an additional rubber or halogenated rubber component.
BACKGROUND
Most conventional elastomers must be crosslinked, i.e., cured or vulcanized, in order to obtain suitably strong, shaped articles. However, crosslinking introduces relatively permanent bonds among the rubber's polymer molecules. Once these bonds are formed, they prevent adequate flowability for subsequent processing or molding. Thus, it is often desirable to process and mold elastomeric articles prior to curing.
Prior to being crosslinked, however, these elastomers often lack sufficient strength, also known as green strength, for easy handling and processing.
Green strength refers to the cohesiveness and dimensional stability under relatively low stress of a rubber compound before it is vulcanized or cured. Green strength is important in such industries as tire manufacturing, where the innerlining and other layers of the tire may be formed in one stage, while curing takes place in a later stage. Green strength is important in allowing the manufacturer to shape and stretch the uncured elastomer, while maintaining other favorable properties such as low air permeability.
Ionomerization (i.e., ionomer formation) provides a means for modifying green strength without chemical crosslinking (i.e., formation of covalent bonds) through a cure process. Ionomerization of amines is also known in the art as "quaternization", due to the formation of a quaternary amine (ammonium ion).
HAVING IMPROVED STABILITY AND GREEN
STRENGTH
FIELD
The present invention relates generally to elastomeric compositions having improved thermal stability and green strength. These elastomeric compositions include compositions of a halogenated elastomer such as an isoolefin copolymer comprising a halomethylstyrene derived unit, and an am'ine. The composition may also include an additional rubber or halogenated rubber component.
BACKGROUND
Most conventional elastomers must be crosslinked, i.e., cured or vulcanized, in order to obtain suitably strong, shaped articles. However, crosslinking introduces relatively permanent bonds among the rubber's polymer molecules. Once these bonds are formed, they prevent adequate flowability for subsequent processing or molding. Thus, it is often desirable to process and mold elastomeric articles prior to curing.
Prior to being crosslinked, however, these elastomers often lack sufficient strength, also known as green strength, for easy handling and processing.
Green strength refers to the cohesiveness and dimensional stability under relatively low stress of a rubber compound before it is vulcanized or cured. Green strength is important in such industries as tire manufacturing, where the innerlining and other layers of the tire may be formed in one stage, while curing takes place in a later stage. Green strength is important in allowing the manufacturer to shape and stretch the uncured elastomer, while maintaining other favorable properties such as low air permeability.
Ionomerization (i.e., ionomer formation) provides a means for modifying green strength without chemical crosslinking (i.e., formation of covalent bonds) through a cure process. Ionomerization of amines is also known in the art as "quaternization", due to the formation of a quaternary amine (ammonium ion).
Since it is a reversible process, ionomerization provides green strength at lower temperature as well as good processability at higher temperatures. A typical method of ionomerization is the addition of tertiary amines to the elastomer compositions, the basic amine functionality interacting with a more acidic functional group on the polymer in order to form stable interactions that increase green strength. US 3,898,253 and 4,256,8576 generally describe the use of tertiary amines to directly modify halobutyl rubber compositions to improve their green strength. However, halobutyl rubber, such as bromobutyl rubber, is not very reactive with these amines. Therefore, the mixture must be heated for a substantial period of time in order to obtain sufficient green strength.
SUMMARY
The present inventors have found that elastomer green strength and/or thermal stability in elastomers, especially halogenated elastomers, is greatly improved by blending the rubber with an amine or phosphine and an isoolefin copolymer comprising a halomethylstyrene derived unit. The combined elastomer and amine, for purposes of this description, may be the to form an "ionomer"
or "ionomer composition". The formation of the ionomer can be in situ and with little or no heating.
The present invention is a composition and a method of forming a composition, the composition comprising at least two components. An additional rubber component may additionally be present in the composition of the invention. In one embodiment, the first component is an isoolefin copolymer comprising a halomethylstyrene derived unit. This copolymer is present in the composition from 95% to 5% by weight of the composition. The halogen may be any halogen, desirably chlorine or bromine.
In one embodiment, the isoolefin has between 4 and 7 carbon atoms and the copolymer includes from 0.5% to 20% by weight p-alkylstyrene, wherein from 0.01 mole % to 60 mole % of the methyl groups present on the benzene ring of the p-alkylstyrene contain a halogen atom. In a preferred embodiment, isoolefin copolymer is an EXXPROTM Elastomer (ExxonMobil Chemical Company, Houston TX).
The amine or phosphine compound represented by the formula (R1R2R3)Q, wherein Q is a Group 15 element, preferably nitrogen or phosphorous, and wherein Rl is either hydrogen or a C4 to C30 hydrocarbyl group, R2 is either hydrogen or a C1 to C30 hydrocarbyl group; and R3 is either hydrogen or a C1 to C30 hydrocarbyl group provided that at least one of Rl, R2 and R3 is not hydrogen. The amine is present from 0.1 to 5 % by weight of the composition. In another embodiment, the composition contains the amine from 0.1 mole % to 60 mole % relative to the mole % of halogen atom present in the composition.
When present, an additional elastomeric component (hereinafter referred to as a "rubber" or "rubber component") may be included in the composition from 5% to 95% by weight of the composition. The additional rubber is selected from butyl rubber, halogenated butyl rubber, star-branched butyl rubber, halogenated star-branched butyl rubber, isobutylene homopolymer, butadiene rubber, neoprene, nitrile rubbers, ethylene/propylene/diene terpolymers, ethylene/propylene copolymers, styrene butadiene rubbers, polybutadiene, polyisoprene, isoolefin/alkylstyrene copolymer, halogenated isoolefin/alkylstyrene copolymer, natural rubber, polypropylene, polyethylene, polyurethane, polyvinyl chloride, silicon rubber, propylene oxide polymer, and mixtures thereof.
DETAILED DESCRIPTION
The composition of the present invention include at least two components:
an isoolefin copolymer comprising a halomethylstyrene derived unit and an amine or phosphine component. In another embodiment, an additional rubber may be present. The invention also includes a method of forming the composition with the amine and other components. The composition is initially uncured (or unvulcanized) when combined, but may also be cured to form a cured composition.
As used herein, in reference to Periodic Table "Groups", the new numbering scheme for the Periodic Table Groups are used as in HAWLEY'S
CONDENSED CHEMICAL DICTIONARY 852 (13th ed. 1997).
The term "elastomer", as used herein, refers to any polymer or composition of polymers consistent with the ASTM D1566 definition. The term "elastomer" may be used interchangeably with the term "rubber", as used herein.
Isoolefin copolymer comprising a halomethylstyrene derived unit Compositions of the present invention include at least one halogenated elastomer. The halogenated elastomer in one embodiment of the invention is a random copolymer of comprising at least C4 to C7 isoolefin derived units, such as isobutylene derived units, and halomethylstyrene derived units. The halomethylstyrene unit may be an ortho-, meta-, or para-alkyl-substituted styrene unit. In one embodiment, the halomethylstyrene derived unit is a p-halomethylstyrene containing at least 80%, more preferably at least 90% by weight of the para-isomer. The "halo" group can be any halogen, desirably chlorine or bromine. The halogenated elastomer may also include functionalized interpolymers wherein at least some of the alkyl substituents groups present in the styrene monomer units contain benzylic halogen or some other functional group described further below. These interpolymers are herein referred to as "isoolefin copolymers comprising a halomethylstyrene derived unit" or simply "isoolefin copolymer".
The isoolefin copolymer may also include other monomer derived units.
The isoolefin of the copolymer may be a C4 to C12 compound, non-limiting examples of which are compounds such as isobutylene, isobutene, 2-methyl-l-butene, 3-methyl-l-butene, 2-methyl-2-butene, 1-butene, 2-butene, methyl vinyl ether, indene, vinyltrimethylsilane, hexene, and 4-methyl-l-pentene. The copolymer may also further comprise multiolefin derived units. The multiolefin is a C4 to C14 multiolefin such as isoprene, butadiene, 2,3-dimethyl-1,3-butadiene, myrcene, 6,6-dimethyl-fulvene, hexadiene, cyclopentadiene, and piperylene, and other monomers such as disclosed in EP 0 279 456 and US 5,506,316 and 5 5,162,425. Desirable styrenic monomer derived units that may comprise the copolymer include styrene, methylstyrene, chlorostyrene, methoxystyrene, indene and indene derivatives, and combinations thereof.
In another embodiment of the invention, the interpolymer is a random elastomeric copolymer of an ethylene derived unit or a C3 to C6 a-olefin derived unit and an halomethylstyrene derived unit, preferably p-halomethylstyrene containing at least 80%, more preferably at least 90% by weight of the para-isomer and also include functionalized interpolymers wherein at least some of the alkyl substituents groups present in the styrene monomer units contain benzylic halogen or some other functional group.
Preferred isoolefin copolymers may be characterized as interpolymers containing the following monomer units randomly spaced along the polymer chain:
1. 2.
H H
I -CHz uv` ~vw I -CHZnnnn R-C H R-i X
I
R1 R, wherein R and R' are independently hydrogen, lower alkyl, preferably C1 to C7 alkyl and primary or secondary alkyl halides and X is a functional group such as halogen. Desirable halogens are chlorine, bromine or combinations thereof.
SUMMARY
The present inventors have found that elastomer green strength and/or thermal stability in elastomers, especially halogenated elastomers, is greatly improved by blending the rubber with an amine or phosphine and an isoolefin copolymer comprising a halomethylstyrene derived unit. The combined elastomer and amine, for purposes of this description, may be the to form an "ionomer"
or "ionomer composition". The formation of the ionomer can be in situ and with little or no heating.
The present invention is a composition and a method of forming a composition, the composition comprising at least two components. An additional rubber component may additionally be present in the composition of the invention. In one embodiment, the first component is an isoolefin copolymer comprising a halomethylstyrene derived unit. This copolymer is present in the composition from 95% to 5% by weight of the composition. The halogen may be any halogen, desirably chlorine or bromine.
In one embodiment, the isoolefin has between 4 and 7 carbon atoms and the copolymer includes from 0.5% to 20% by weight p-alkylstyrene, wherein from 0.01 mole % to 60 mole % of the methyl groups present on the benzene ring of the p-alkylstyrene contain a halogen atom. In a preferred embodiment, isoolefin copolymer is an EXXPROTM Elastomer (ExxonMobil Chemical Company, Houston TX).
The amine or phosphine compound represented by the formula (R1R2R3)Q, wherein Q is a Group 15 element, preferably nitrogen or phosphorous, and wherein Rl is either hydrogen or a C4 to C30 hydrocarbyl group, R2 is either hydrogen or a C1 to C30 hydrocarbyl group; and R3 is either hydrogen or a C1 to C30 hydrocarbyl group provided that at least one of Rl, R2 and R3 is not hydrogen. The amine is present from 0.1 to 5 % by weight of the composition. In another embodiment, the composition contains the amine from 0.1 mole % to 60 mole % relative to the mole % of halogen atom present in the composition.
When present, an additional elastomeric component (hereinafter referred to as a "rubber" or "rubber component") may be included in the composition from 5% to 95% by weight of the composition. The additional rubber is selected from butyl rubber, halogenated butyl rubber, star-branched butyl rubber, halogenated star-branched butyl rubber, isobutylene homopolymer, butadiene rubber, neoprene, nitrile rubbers, ethylene/propylene/diene terpolymers, ethylene/propylene copolymers, styrene butadiene rubbers, polybutadiene, polyisoprene, isoolefin/alkylstyrene copolymer, halogenated isoolefin/alkylstyrene copolymer, natural rubber, polypropylene, polyethylene, polyurethane, polyvinyl chloride, silicon rubber, propylene oxide polymer, and mixtures thereof.
DETAILED DESCRIPTION
The composition of the present invention include at least two components:
an isoolefin copolymer comprising a halomethylstyrene derived unit and an amine or phosphine component. In another embodiment, an additional rubber may be present. The invention also includes a method of forming the composition with the amine and other components. The composition is initially uncured (or unvulcanized) when combined, but may also be cured to form a cured composition.
As used herein, in reference to Periodic Table "Groups", the new numbering scheme for the Periodic Table Groups are used as in HAWLEY'S
CONDENSED CHEMICAL DICTIONARY 852 (13th ed. 1997).
The term "elastomer", as used herein, refers to any polymer or composition of polymers consistent with the ASTM D1566 definition. The term "elastomer" may be used interchangeably with the term "rubber", as used herein.
Isoolefin copolymer comprising a halomethylstyrene derived unit Compositions of the present invention include at least one halogenated elastomer. The halogenated elastomer in one embodiment of the invention is a random copolymer of comprising at least C4 to C7 isoolefin derived units, such as isobutylene derived units, and halomethylstyrene derived units. The halomethylstyrene unit may be an ortho-, meta-, or para-alkyl-substituted styrene unit. In one embodiment, the halomethylstyrene derived unit is a p-halomethylstyrene containing at least 80%, more preferably at least 90% by weight of the para-isomer. The "halo" group can be any halogen, desirably chlorine or bromine. The halogenated elastomer may also include functionalized interpolymers wherein at least some of the alkyl substituents groups present in the styrene monomer units contain benzylic halogen or some other functional group described further below. These interpolymers are herein referred to as "isoolefin copolymers comprising a halomethylstyrene derived unit" or simply "isoolefin copolymer".
The isoolefin copolymer may also include other monomer derived units.
The isoolefin of the copolymer may be a C4 to C12 compound, non-limiting examples of which are compounds such as isobutylene, isobutene, 2-methyl-l-butene, 3-methyl-l-butene, 2-methyl-2-butene, 1-butene, 2-butene, methyl vinyl ether, indene, vinyltrimethylsilane, hexene, and 4-methyl-l-pentene. The copolymer may also further comprise multiolefin derived units. The multiolefin is a C4 to C14 multiolefin such as isoprene, butadiene, 2,3-dimethyl-1,3-butadiene, myrcene, 6,6-dimethyl-fulvene, hexadiene, cyclopentadiene, and piperylene, and other monomers such as disclosed in EP 0 279 456 and US 5,506,316 and 5 5,162,425. Desirable styrenic monomer derived units that may comprise the copolymer include styrene, methylstyrene, chlorostyrene, methoxystyrene, indene and indene derivatives, and combinations thereof.
In another embodiment of the invention, the interpolymer is a random elastomeric copolymer of an ethylene derived unit or a C3 to C6 a-olefin derived unit and an halomethylstyrene derived unit, preferably p-halomethylstyrene containing at least 80%, more preferably at least 90% by weight of the para-isomer and also include functionalized interpolymers wherein at least some of the alkyl substituents groups present in the styrene monomer units contain benzylic halogen or some other functional group.
Preferred isoolefin copolymers may be characterized as interpolymers containing the following monomer units randomly spaced along the polymer chain:
1. 2.
H H
I -CHz uv` ~vw I -CHZnnnn R-C H R-i X
I
R1 R, wherein R and R' are independently hydrogen, lower alkyl, preferably C1 to C7 alkyl and primary or secondary alkyl halides and X is a functional group such as halogen. Desirable halogens are chlorine, bromine or combinations thereof.
Preferably R and R' are each hydrogen. The -CRR1H and -CRR1X groups can be substituted on the styrene ring in either the ortho, meta, or para positions, preferably para. Up to 60 mole % of the p-substituted styrene present in the interpolymer structure may be the functionalized structure (2) above in one embodiment, and in another embodiment from 0.1 to 5 mol%. In yet another embodiment, the amount of functionalized structure (2) is from 0.4 to 1 mol%.
The functional group X may be halogen or some other functional group which may be incorporated by nucleophilic substitution of benzylic halogen with other groups such as carboxylic acids; carboxy salts; carboxy esters, amides and imides; hydroxy; alkoxide; phenoxide; thiolate; thioether; xanthate; cyanide;
cyanate; amino and mixtures thereof. These functionalized isomonoolefin copolymers, their method of preparation, methods of functionalization, and cure are more particularly disclosed in US 5,162,445.
Most useful of such functionalized materials are elastomeric random interpolymers of isobutylene and p-methylstyrene containing from 0.5 to 20 mole % p-methylstyrene wherein up to 60 mole% of the methyl substituent groups present on the benzyl ring contain a bromine or chlorine atom, preferably a bromine atom (p-bromomethylstyrene), as well as acid or ester functionalized versions thereof wherein the halogen atom has been displaced by maleic anhydride or by acrylic or methacrylic acid functionality. These interpolymers are termed "halogenated poly(isobutylene-co p-methylstyrene)" or "brominated poly(isobutylene-co-p-methylstyrene)", and are commercially available under the name EXXPROTM Elastomers (ExxonMobil Chemical Company, Houston TX). It is understood that the use of the terms "halogenated" or "brominated" are not limited to the method of halogenation of the copolymer, but merely descriptive of the copolymer which comprises the isobutylene derived units, the p-methylstyrene derived units, and the p-halomethylstyrene derived units.
These functionalized polymers preferably have a substantially homogeneous compositional distribution such that at least 95% by weight of the polymer has a p-alkylstyrene content witliin 10% of the average p-alkylstyrene content of the polymer. More preferred polymers are also characterized by a narrow molecular weight distribution (Mw/Mn) of less than 5, more preferably less than 2.5, a preferred viscosity average molecular weight in the range of from 200,000 up to 2,000,000 and a preferred number average molecular weight in the range of from 25,000 to 750,000 as determined by gel permeation chromatography.
The copolymers may be prepared by a slurry polymerization of the monomer mixture using a Lewis acid catalyst, followed by halogenation, preferably bromination, in solution in the presence of halogen and a radical initiator such as heat and/or light and/or a chemical initiator and, optionally, followed by electrophilic substitution of bromine with a different functional derived unit.
Preferred halogenated poly(isobutylene-co-p-methylstyrene) are brominated polymers which generally contain from 0.1 to 5 wt% of bromomethyl groups. In yet another embodiment, the amount of bromomethyl groups is from 0.2 to 2.5 wt%. Expressed another way, preferred copolymers contain from 0.05 up to 2.5 mole% of bromine, based on the weight of the polymer, more preferably from 0.1 to 1.25 mole % bromine, and are substantially free of ring halogen or halogen in the polymer backbone chain. In one embodiment of the invention, the interpolymer is a copolymer of C4 to C7 isomonoolefin derived units, a p-methylstyrene derived units and a p-halomethylstyrene derived units, wherein the p-halomethylstyrene units are present in the interpolymer from 0.4 to 1 mol%
based on the interpolymer. In another embodiment, the p-halomethylstyrene is p-bromomethylstyrene. The Mooney Viscosity (1+8, 125 C, ASTM D1646, modified) is from 30 to 60 MU.
Amine/Phosphine Component The amines or phosphines that are incorporated into the compositions of the invention are represented by the formula (R1R2R3)Q, wherein Q is a Group 15 element, preferably nitrogen or phosphorous, and wherein Rl is either hydrogen or a C4 to C30 hydrocarbyl group, R2 is either hydrogen or a C1 to liydrocarbyl group, and R3 is either hydrogen or a C1 to C30, preferably a C1 to C8, hydrocarbyl group, provided that at least one of Rl, R2 and R3 is not hydrogen. Preferably, R3 is a methyl or ethyl group and one of R1 or R2 is a to C20 hydrocarbyl group and the other is a methyl or ethyl group. The hydrocarbyl groups, independently, may be saturated, unsaturated, cyclic or aromatic.
Any amine may be used so long as it is sufficiently compatible with the rubber component, and the isoolefin copolymer, and as long as permanent crosslinking is avoided. When improved green strength is desired, preferably, the amine component is one capable of ionomerizing the copolymer component. In one desirable einbodiment, such amines may be more hindered and may be represented by the formula (R1R2R3)N wherein Rl and R2 are independently a C4 to C30 hydrocarbyl group and R3 is either hydrogen or a C1 to C30 hydrocarbyl group.
Examples of suitable amine components include, but are not limited to: N, N-dimethyl hexadecylamine, N,N-dimethyl hexylamine, N,N-dimethyl dodecylamine, N,N-dimethyl octadecylamine, N,N-diethyl decylamine, N,N-dimethylbenzylamine, N,N-methyl propyl hexadecylamine, and morpholine.
The isoolefin copolymer, amine, and when present, the rubber components, are combined in amounts effective to produce the desired improvement in green strength and/or stability. The precise concentrations of each component will thus depend on the specific components used. The relative amounts of rubber and amine will generally dictate the degree the properties of the composition are influenced. When a halogenated rubber component is used, for example, the preferred amine level is from 0.05 to 2 mole equivalents of amine per rubber or isoolefin copolymer halogen, more preferably from 0.1 to 1 mole equivalent of amine per rubber or copolymer halogen.
The present invention is particularly effective when compositions of an isoolefin copolymer and another rubber are employed. The relative amounts of the isoolefin copolymer, amine or phosphine, and when present, the rubber component, will depend on the particular rubber component used. Preferably, only so much amine or phosphine and copolymer is used as is needed to improve green strength and/or stability to the desired degree. For example, the weight percent of the rubber component may vary from as little as 5% to up to 95% by weight of the composition, more preferably from 10% to 90% by weight of the composition, even more preferably from 20% to 80% by weight of the composition.
The method used to combine the at least two components is not critical as long as there is adequate dispersion of the amine and other components within the rubber. Thus, any mixing device may be used. In one embodiment, the components are combined and mixed at from 20 to 200 C. The mixing may be facilitated by heating the mixture from 50 C up to 200 C, and from 50 C up to 150 C in another embodiment in an internal mixer or rubber mill. Notably, it is not necessary to .heat the mixture and/or mix for extended periods of time after mixing is achieved in order to obtain adequate ionomerization. Once the components are mixed, additional mixing or heating time for reaction should not be necessary.
The mixing order is not critical. For convenience, the at least two components may be mixed at one time. Alternatively, the rubber component and amine (and other components when present) may be combined first, followed by addition of the isoolefin copolymer. For some applications, it may be desirable to pre-composition the amine and rubber and then add the isoolefin copolymer, or pre-composition the isoolefin copolymer and rubber followed by the amine.
Various additives may be used in suitable amounts. For example, various reinforcing agents or fillers such as carbon black, clay, silica, talc, and the like may be combined with the composition at any point during production. Various colorants may be added such as titanium dioxide, carbon black, etc. Other 5 additives include antioxidants, stabilizers, processing oils, lubricants, anti-static agents, waxes, flame retardants and plasticizers.
After the isoolefin copolymer, amine, and when present, the rubber, are combined, the composition having improved green strength-may be used directly 10 in molded, extruded or shaped articles. It may be necessary to heat the composition in order to obtain the necessary viscosity for molding.
Additional Rubber component An additional elastomeric or "rubber" component may be included in compositions of the invention. The term "rubber" or "rubber component" as used herein may include, but is not in any way limited to, the following polymers:
butyl rubber, halogenated butyl rubber, star-branched butyl rubber, halogenated star-branched butyl rubber, isobutylene homopolymer, butadiene rubber, neoprene, nitrile rubbers, ethylene/propylene/diene terpolymers, ethylene/propylene copolymers, styrene butadiene rubbers, polybutadiene, polyisoprene, isoolefin/alkylstyrene copolymer, halogenated isoolefin/alkylstyrene copolymer, natural rubber, polypropylene, polyethylene, polyurethane, polyvinyl chloride, silicon rubber, propylene oxide polymer, and mixtures thereof. Other suitable rubbers are disclosed in, for example, RUBBER TECHNOLOGY (Maurice Morton, ed., Chapman & Hall 1995), and are well known in the art.
As used herein the term "butyl rubber" is defined to mean a polymer predominately comprised of repeat units of isobutylene but including a few repeat units of a multiolefin. Preferably from 85% to 99.5% by weight of the butyl rubber are repeat units derived from the polymerization of isobutylene, while from 0.1% to 15% by weight of the repeat units are derived from a multiolefin having from 4 to 8 carbon atoms such as butadiene, isoprene, hexadiene, etc., with isoprene being preferred.
"Halogenated butyl rubber" is defined to mean butyl rubber that contains at least 0.05% by weight halogen such as chlorine or bromine, preferably bromine.
Preferred halogenated butyl rubbers are those that contain from 0.1% to 15% by weight halogen, more preferably from 0.5% to 10.0% by weight halogen based on the total weight of the halogenated polymer. Numerous patents disclose halogenated butyl rubber containing various amounts of chemically bound halogen, see for example, US 2,631,984, 2,732,354, 3,099,644, 2,944,578, 3,943,664, 2,964,489, and 4,130,534.
As used herein "nitrile rubbers" are copolymers of acrylonitrile with a conjugated dierie having from 4 to 8 carbon atoms, with butadiene being preferred.
As used herein, "ethylene/propylene copolymers" are defined to mean those elastomeric or thermoplastic curable copolymers comprising ethylene and propylene. The preferred ethylene/propylene copolymer is one in which the ethylene component is between 20 and 90 % by weight of the copolymer.
As used herein, "ethylene/propylene/diene terpolymers" are defined as those elastomeric or thermoplastic curable terpolymers comprising ethylene, propylene and diene units. Preferred diene units are 5-ethylidene norbornene, methylidene norbornene, dicyclopentadiene, 1,4-hexadiene and 5-vinyl norbornene.
As used herein, "isoolefin/alkylstyrene copolymers" and "halogenated isoolefin/alkylstyrene copolymers" refer to copolymers comprising an isoolefin and an alkylstyrene, preferably a methylstyrene.
Cure Agents and Accelerators The compositions may also be cured using conventional curing or vulcanizing agents. Examples include sulfur and sulfur vulcanizing agents; various organic peroxides such as benzoylperoxide, dicumylperoxide, 2,5-dimethyl-2,5 di(tertbutylperoxy)hexane, and 2,2'-bis(tertbutylperoxy) diisopropyl benzene;
hydrosilation curing agents; metal oxides such as zinc oxide or magnesium oxide, or organic zinc salts such as zinc stearate; diamines; co-curing agents such as various maleimides; and the like; all as set forth in US 5,073,597. Moreover, various phenolic resins known to the art and to the literature can be utilized, as well as various phenol-formaldehyde resins as set forth in "The Chemistry of Phenol-Formaldehyde Resin Vulcanization of EPDM: Part I. Evidence for Methylene Crosslinks," by Martin Van Duin and Aniko Souphanthong, 68 RUBBER CHEMISTRY AND TECHNOLOGY 717-727 (1995).
The amount of the curing agent will generally vary depending upon the type utilized and especially the desired degree of cure, as is well recognized in the art. For example, the amount of sulfur is generally from 1 to 5, and preferably from 2 to 3 parts by weight per 100 parts by weight of the composition. The amount of the peroxide curing agent is generally from 0.1 to 2.0 parts by weight, the amount of the phenolic curing resin is generally from 2 to 10 parts by weight, and the amount of the hindered amine is from 0.1 to 2 parts by weight, all based upon 100 parts by weight of the composition.
Whenever a halogenated butyl rubber or any halogenated rubber is utilized, a small amount of an alkaline earth oxide compound such as magnesium oxide is utilized in an amount of 3 phr or less, and desirably 2 phr or less for every 100 phr of the halogenated rubber. The alkaline earth oxide is added to act as a scavenger of hydrogen halides.
Conventional catalysts (accelerators) can also be utilized such as those known to the art and to the literature. For example, suitable amounts of various Friedel-Crafts catalysts can be utilized such as stannous chloride, salicylic acid, p-toluene sulfonic acid, zinc chloride, and the like.
The amount of the curative and accelerators are such that a degree of cure, that is, at least 90%, desirably at least 95 or 96%, preferably at least 97%
or 98%
of the curable rubber is non-extractable in a suitable solvent for the particular rubber at 23 C. Suitable solvents include xylene, cyclohexane, acetone, hexane, toluene, and the like.
It has surprisingly been found that, once the compositions are cured, they demonstrate improved thermal and aging stabilization when the composition of the present invention is cured. Thus, not only is green strength improved, the overall characteristics of the cured rubber product are improved.
The compositions of this invention have a wide variety of ultimate uses.
For example, tubings, hoses, gaskets, diaphragms, tires, innerliners, films, bumpers, membranes, adhesives, innertubes and other items where rubbers or rubber-copolymer compositions are employed.
The following examples are presented to illustrate the foregoing discussion. Although the examples may be directed to certain embodiments of the present invention, they are not to be viewed as limiting the invention in any specific respect.
Example 1 A series of compounds shown in Table 1 were prepared according to the following details. Two elastomers from ExxonMobil Chemical were used:
Bromobutyl 2222 specified to contain 2 wt% of bromine and having a Mooney viscosity of 32 at 125 C (1+8) (ASTM D1646 modified), and EXXPROTM 89-1 Elastomer (ExxonMobil Chemical Company, Houston TX), a brominated poly(isobutylene-co-p-methylstyrene) having 0.75 mole % bromine, or 1.2 wt%
The functional group X may be halogen or some other functional group which may be incorporated by nucleophilic substitution of benzylic halogen with other groups such as carboxylic acids; carboxy salts; carboxy esters, amides and imides; hydroxy; alkoxide; phenoxide; thiolate; thioether; xanthate; cyanide;
cyanate; amino and mixtures thereof. These functionalized isomonoolefin copolymers, their method of preparation, methods of functionalization, and cure are more particularly disclosed in US 5,162,445.
Most useful of such functionalized materials are elastomeric random interpolymers of isobutylene and p-methylstyrene containing from 0.5 to 20 mole % p-methylstyrene wherein up to 60 mole% of the methyl substituent groups present on the benzyl ring contain a bromine or chlorine atom, preferably a bromine atom (p-bromomethylstyrene), as well as acid or ester functionalized versions thereof wherein the halogen atom has been displaced by maleic anhydride or by acrylic or methacrylic acid functionality. These interpolymers are termed "halogenated poly(isobutylene-co p-methylstyrene)" or "brominated poly(isobutylene-co-p-methylstyrene)", and are commercially available under the name EXXPROTM Elastomers (ExxonMobil Chemical Company, Houston TX). It is understood that the use of the terms "halogenated" or "brominated" are not limited to the method of halogenation of the copolymer, but merely descriptive of the copolymer which comprises the isobutylene derived units, the p-methylstyrene derived units, and the p-halomethylstyrene derived units.
These functionalized polymers preferably have a substantially homogeneous compositional distribution such that at least 95% by weight of the polymer has a p-alkylstyrene content witliin 10% of the average p-alkylstyrene content of the polymer. More preferred polymers are also characterized by a narrow molecular weight distribution (Mw/Mn) of less than 5, more preferably less than 2.5, a preferred viscosity average molecular weight in the range of from 200,000 up to 2,000,000 and a preferred number average molecular weight in the range of from 25,000 to 750,000 as determined by gel permeation chromatography.
The copolymers may be prepared by a slurry polymerization of the monomer mixture using a Lewis acid catalyst, followed by halogenation, preferably bromination, in solution in the presence of halogen and a radical initiator such as heat and/or light and/or a chemical initiator and, optionally, followed by electrophilic substitution of bromine with a different functional derived unit.
Preferred halogenated poly(isobutylene-co-p-methylstyrene) are brominated polymers which generally contain from 0.1 to 5 wt% of bromomethyl groups. In yet another embodiment, the amount of bromomethyl groups is from 0.2 to 2.5 wt%. Expressed another way, preferred copolymers contain from 0.05 up to 2.5 mole% of bromine, based on the weight of the polymer, more preferably from 0.1 to 1.25 mole % bromine, and are substantially free of ring halogen or halogen in the polymer backbone chain. In one embodiment of the invention, the interpolymer is a copolymer of C4 to C7 isomonoolefin derived units, a p-methylstyrene derived units and a p-halomethylstyrene derived units, wherein the p-halomethylstyrene units are present in the interpolymer from 0.4 to 1 mol%
based on the interpolymer. In another embodiment, the p-halomethylstyrene is p-bromomethylstyrene. The Mooney Viscosity (1+8, 125 C, ASTM D1646, modified) is from 30 to 60 MU.
Amine/Phosphine Component The amines or phosphines that are incorporated into the compositions of the invention are represented by the formula (R1R2R3)Q, wherein Q is a Group 15 element, preferably nitrogen or phosphorous, and wherein Rl is either hydrogen or a C4 to C30 hydrocarbyl group, R2 is either hydrogen or a C1 to liydrocarbyl group, and R3 is either hydrogen or a C1 to C30, preferably a C1 to C8, hydrocarbyl group, provided that at least one of Rl, R2 and R3 is not hydrogen. Preferably, R3 is a methyl or ethyl group and one of R1 or R2 is a to C20 hydrocarbyl group and the other is a methyl or ethyl group. The hydrocarbyl groups, independently, may be saturated, unsaturated, cyclic or aromatic.
Any amine may be used so long as it is sufficiently compatible with the rubber component, and the isoolefin copolymer, and as long as permanent crosslinking is avoided. When improved green strength is desired, preferably, the amine component is one capable of ionomerizing the copolymer component. In one desirable einbodiment, such amines may be more hindered and may be represented by the formula (R1R2R3)N wherein Rl and R2 are independently a C4 to C30 hydrocarbyl group and R3 is either hydrogen or a C1 to C30 hydrocarbyl group.
Examples of suitable amine components include, but are not limited to: N, N-dimethyl hexadecylamine, N,N-dimethyl hexylamine, N,N-dimethyl dodecylamine, N,N-dimethyl octadecylamine, N,N-diethyl decylamine, N,N-dimethylbenzylamine, N,N-methyl propyl hexadecylamine, and morpholine.
The isoolefin copolymer, amine, and when present, the rubber components, are combined in amounts effective to produce the desired improvement in green strength and/or stability. The precise concentrations of each component will thus depend on the specific components used. The relative amounts of rubber and amine will generally dictate the degree the properties of the composition are influenced. When a halogenated rubber component is used, for example, the preferred amine level is from 0.05 to 2 mole equivalents of amine per rubber or isoolefin copolymer halogen, more preferably from 0.1 to 1 mole equivalent of amine per rubber or copolymer halogen.
The present invention is particularly effective when compositions of an isoolefin copolymer and another rubber are employed. The relative amounts of the isoolefin copolymer, amine or phosphine, and when present, the rubber component, will depend on the particular rubber component used. Preferably, only so much amine or phosphine and copolymer is used as is needed to improve green strength and/or stability to the desired degree. For example, the weight percent of the rubber component may vary from as little as 5% to up to 95% by weight of the composition, more preferably from 10% to 90% by weight of the composition, even more preferably from 20% to 80% by weight of the composition.
The method used to combine the at least two components is not critical as long as there is adequate dispersion of the amine and other components within the rubber. Thus, any mixing device may be used. In one embodiment, the components are combined and mixed at from 20 to 200 C. The mixing may be facilitated by heating the mixture from 50 C up to 200 C, and from 50 C up to 150 C in another embodiment in an internal mixer or rubber mill. Notably, it is not necessary to .heat the mixture and/or mix for extended periods of time after mixing is achieved in order to obtain adequate ionomerization. Once the components are mixed, additional mixing or heating time for reaction should not be necessary.
The mixing order is not critical. For convenience, the at least two components may be mixed at one time. Alternatively, the rubber component and amine (and other components when present) may be combined first, followed by addition of the isoolefin copolymer. For some applications, it may be desirable to pre-composition the amine and rubber and then add the isoolefin copolymer, or pre-composition the isoolefin copolymer and rubber followed by the amine.
Various additives may be used in suitable amounts. For example, various reinforcing agents or fillers such as carbon black, clay, silica, talc, and the like may be combined with the composition at any point during production. Various colorants may be added such as titanium dioxide, carbon black, etc. Other 5 additives include antioxidants, stabilizers, processing oils, lubricants, anti-static agents, waxes, flame retardants and plasticizers.
After the isoolefin copolymer, amine, and when present, the rubber, are combined, the composition having improved green strength-may be used directly 10 in molded, extruded or shaped articles. It may be necessary to heat the composition in order to obtain the necessary viscosity for molding.
Additional Rubber component An additional elastomeric or "rubber" component may be included in compositions of the invention. The term "rubber" or "rubber component" as used herein may include, but is not in any way limited to, the following polymers:
butyl rubber, halogenated butyl rubber, star-branched butyl rubber, halogenated star-branched butyl rubber, isobutylene homopolymer, butadiene rubber, neoprene, nitrile rubbers, ethylene/propylene/diene terpolymers, ethylene/propylene copolymers, styrene butadiene rubbers, polybutadiene, polyisoprene, isoolefin/alkylstyrene copolymer, halogenated isoolefin/alkylstyrene copolymer, natural rubber, polypropylene, polyethylene, polyurethane, polyvinyl chloride, silicon rubber, propylene oxide polymer, and mixtures thereof. Other suitable rubbers are disclosed in, for example, RUBBER TECHNOLOGY (Maurice Morton, ed., Chapman & Hall 1995), and are well known in the art.
As used herein the term "butyl rubber" is defined to mean a polymer predominately comprised of repeat units of isobutylene but including a few repeat units of a multiolefin. Preferably from 85% to 99.5% by weight of the butyl rubber are repeat units derived from the polymerization of isobutylene, while from 0.1% to 15% by weight of the repeat units are derived from a multiolefin having from 4 to 8 carbon atoms such as butadiene, isoprene, hexadiene, etc., with isoprene being preferred.
"Halogenated butyl rubber" is defined to mean butyl rubber that contains at least 0.05% by weight halogen such as chlorine or bromine, preferably bromine.
Preferred halogenated butyl rubbers are those that contain from 0.1% to 15% by weight halogen, more preferably from 0.5% to 10.0% by weight halogen based on the total weight of the halogenated polymer. Numerous patents disclose halogenated butyl rubber containing various amounts of chemically bound halogen, see for example, US 2,631,984, 2,732,354, 3,099,644, 2,944,578, 3,943,664, 2,964,489, and 4,130,534.
As used herein "nitrile rubbers" are copolymers of acrylonitrile with a conjugated dierie having from 4 to 8 carbon atoms, with butadiene being preferred.
As used herein, "ethylene/propylene copolymers" are defined to mean those elastomeric or thermoplastic curable copolymers comprising ethylene and propylene. The preferred ethylene/propylene copolymer is one in which the ethylene component is between 20 and 90 % by weight of the copolymer.
As used herein, "ethylene/propylene/diene terpolymers" are defined as those elastomeric or thermoplastic curable terpolymers comprising ethylene, propylene and diene units. Preferred diene units are 5-ethylidene norbornene, methylidene norbornene, dicyclopentadiene, 1,4-hexadiene and 5-vinyl norbornene.
As used herein, "isoolefin/alkylstyrene copolymers" and "halogenated isoolefin/alkylstyrene copolymers" refer to copolymers comprising an isoolefin and an alkylstyrene, preferably a methylstyrene.
Cure Agents and Accelerators The compositions may also be cured using conventional curing or vulcanizing agents. Examples include sulfur and sulfur vulcanizing agents; various organic peroxides such as benzoylperoxide, dicumylperoxide, 2,5-dimethyl-2,5 di(tertbutylperoxy)hexane, and 2,2'-bis(tertbutylperoxy) diisopropyl benzene;
hydrosilation curing agents; metal oxides such as zinc oxide or magnesium oxide, or organic zinc salts such as zinc stearate; diamines; co-curing agents such as various maleimides; and the like; all as set forth in US 5,073,597. Moreover, various phenolic resins known to the art and to the literature can be utilized, as well as various phenol-formaldehyde resins as set forth in "The Chemistry of Phenol-Formaldehyde Resin Vulcanization of EPDM: Part I. Evidence for Methylene Crosslinks," by Martin Van Duin and Aniko Souphanthong, 68 RUBBER CHEMISTRY AND TECHNOLOGY 717-727 (1995).
The amount of the curing agent will generally vary depending upon the type utilized and especially the desired degree of cure, as is well recognized in the art. For example, the amount of sulfur is generally from 1 to 5, and preferably from 2 to 3 parts by weight per 100 parts by weight of the composition. The amount of the peroxide curing agent is generally from 0.1 to 2.0 parts by weight, the amount of the phenolic curing resin is generally from 2 to 10 parts by weight, and the amount of the hindered amine is from 0.1 to 2 parts by weight, all based upon 100 parts by weight of the composition.
Whenever a halogenated butyl rubber or any halogenated rubber is utilized, a small amount of an alkaline earth oxide compound such as magnesium oxide is utilized in an amount of 3 phr or less, and desirably 2 phr or less for every 100 phr of the halogenated rubber. The alkaline earth oxide is added to act as a scavenger of hydrogen halides.
Conventional catalysts (accelerators) can also be utilized such as those known to the art and to the literature. For example, suitable amounts of various Friedel-Crafts catalysts can be utilized such as stannous chloride, salicylic acid, p-toluene sulfonic acid, zinc chloride, and the like.
The amount of the curative and accelerators are such that a degree of cure, that is, at least 90%, desirably at least 95 or 96%, preferably at least 97%
or 98%
of the curable rubber is non-extractable in a suitable solvent for the particular rubber at 23 C. Suitable solvents include xylene, cyclohexane, acetone, hexane, toluene, and the like.
It has surprisingly been found that, once the compositions are cured, they demonstrate improved thermal and aging stabilization when the composition of the present invention is cured. Thus, not only is green strength improved, the overall characteristics of the cured rubber product are improved.
The compositions of this invention have a wide variety of ultimate uses.
For example, tubings, hoses, gaskets, diaphragms, tires, innerliners, films, bumpers, membranes, adhesives, innertubes and other items where rubbers or rubber-copolymer compositions are employed.
The following examples are presented to illustrate the foregoing discussion. Although the examples may be directed to certain embodiments of the present invention, they are not to be viewed as limiting the invention in any specific respect.
Example 1 A series of compounds shown in Table 1 were prepared according to the following details. Two elastomers from ExxonMobil Chemical were used:
Bromobutyl 2222 specified to contain 2 wt% of bromine and having a Mooney viscosity of 32 at 125 C (1+8) (ASTM D1646 modified), and EXXPROTM 89-1 Elastomer (ExxonMobil Chemical Company, Houston TX), a brominated poly(isobutylene-co-p-methylstyrene) having 0.75 mole % bromine, or 1.2 wt%
bromine on a 5 wt% p-methylstyrene (PMS) containing polymer having a Mooney viscosity of 35 at 125 C (1+8) (ASTM D1646 modified).
Three Master Batch (MB) compounds were mixed in an internal lab mixer (a BR Banbury mixer by Farrel Co.) incorporating all of the ingredients shown in Table 1, except for the amine ingredient. MB1 (compounds lA through 1D) were based on the bromobutyl elastomer. MB2 (compounds 2A and 2B), and MB3 (compounds 3A and 3B) were based on a mixture of the bromobutyl and EXXPROTM Elastomers. The amine used was a tertiary amine, N,N-dimethylhexadecylamine, Armeen DM16D (Akzo Nobel Co.). The amine was added at the levels shown in Table 1 on a two-roll rubber mill.
The MB mixes had a total batch weigl7t of 1500 g each following the formulations in Table 1(excluding amine). The mixer was operated at 100 RPM
with 60 C water circulated through the mixer walls. The elastomers were added to the mixer first with all other ingredients added 30 seconds after introduction of the elastomers into the mixer. The mixed compounds were removed from the mixer when the compound temperature reached 150 C.
The MB ingredients shown in Table 1 other than the ones described above were: a paraffinic oil, DrakeolTM 35 mineral oil (PenRe Co.); carbon black designated as N 660 black; stearic acid (Witco Co.); Magnesium oxide, MagliteTM
K (C.P. Hall Co.).
The amine described above was added to 350g portions of the three MB
compounds on a lab rubber mill of 6 x 13 inch. (or 15.2 x 33 cm) roll size (KBS
Corp.). The mill had cooling water at 27 C circulated through the rolls. The mill mix procedure started with mixing the MB compounds on the mill following gradual addition of the liquid amine, until it was evenly dispersed by cutting and rolling a number of times.
The compounds of Table 1 were then calendered at a low speed between 2 calender rolls kept at 85 C. The calendering process started by warming up the compounds on the calender to the point the compound stayed smoothly on one roll. Following this, the compound was left on the turning roll for 2 minutes to 5 obtain a homogeneous temperature, after which the compound was removed as a smooth sheet of 3mm thick.
The sheets were pressed into pads of 0.2 x 15 x 15 cm between Mylar polyester film in a 100 C mold. Samples of 0.5 x 3 inch (1.25 x 7.6 cm) were cut 10 for testing.
Green strength was tested using two different Instron testers, one that was equipped with an environmental chamber heated to 40 C. The samples were clamped at linch (2.54cm) distance between the tester clamps. The test was 15 conducted by moving the clamps apart at a speed of 5 in/min (12.7 cm/min) to a 100% extension, a total stretching distance of 1 inch (2.54 cm). The "engineering stress" (force divided by original cross sectional area) at 100% extension was defined as the "green strength", and is shown in Table 1 for 2 testing temperatures, ambient (25 C) and 40 C.
A different portion of 250g each of the calendered samples of Table 1 were additionally mixed with a typical tire innerliner cure package on the lab mill described above. The mill rolls were kept cool by circulating 24 C water through them. The cure ingredients consisted of 3 phr zinc oxide (KadoxTM 930C from Zinc Corporation of America), 0.5 phr sulfur from R.E. Carroll, Inc. and 1.5 phr MBTS (AltaxTM from R.T. Vanderbilt Company, Inc.). The term "phr" (parts per hundred rubber) designates the proportion of the ingredient level per 100 g of the total elastomer or elastomer composition from Table 1. The compounds were then cured in a hot press at 160 C for 18 to 27 minutes at a time equal to 90%
cure time (t90) plus 2 minutes as determined by a curometer test using an ODR 2000E
(Alpha Instruments), operating at 160 C at 3 arc and a standard oscillation rate of 100 cpm, for 60 min.
Three Master Batch (MB) compounds were mixed in an internal lab mixer (a BR Banbury mixer by Farrel Co.) incorporating all of the ingredients shown in Table 1, except for the amine ingredient. MB1 (compounds lA through 1D) were based on the bromobutyl elastomer. MB2 (compounds 2A and 2B), and MB3 (compounds 3A and 3B) were based on a mixture of the bromobutyl and EXXPROTM Elastomers. The amine used was a tertiary amine, N,N-dimethylhexadecylamine, Armeen DM16D (Akzo Nobel Co.). The amine was added at the levels shown in Table 1 on a two-roll rubber mill.
The MB mixes had a total batch weigl7t of 1500 g each following the formulations in Table 1(excluding amine). The mixer was operated at 100 RPM
with 60 C water circulated through the mixer walls. The elastomers were added to the mixer first with all other ingredients added 30 seconds after introduction of the elastomers into the mixer. The mixed compounds were removed from the mixer when the compound temperature reached 150 C.
The MB ingredients shown in Table 1 other than the ones described above were: a paraffinic oil, DrakeolTM 35 mineral oil (PenRe Co.); carbon black designated as N 660 black; stearic acid (Witco Co.); Magnesium oxide, MagliteTM
K (C.P. Hall Co.).
The amine described above was added to 350g portions of the three MB
compounds on a lab rubber mill of 6 x 13 inch. (or 15.2 x 33 cm) roll size (KBS
Corp.). The mill had cooling water at 27 C circulated through the rolls. The mill mix procedure started with mixing the MB compounds on the mill following gradual addition of the liquid amine, until it was evenly dispersed by cutting and rolling a number of times.
The compounds of Table 1 were then calendered at a low speed between 2 calender rolls kept at 85 C. The calendering process started by warming up the compounds on the calender to the point the compound stayed smoothly on one roll. Following this, the compound was left on the turning roll for 2 minutes to 5 obtain a homogeneous temperature, after which the compound was removed as a smooth sheet of 3mm thick.
The sheets were pressed into pads of 0.2 x 15 x 15 cm between Mylar polyester film in a 100 C mold. Samples of 0.5 x 3 inch (1.25 x 7.6 cm) were cut 10 for testing.
Green strength was tested using two different Instron testers, one that was equipped with an environmental chamber heated to 40 C. The samples were clamped at linch (2.54cm) distance between the tester clamps. The test was 15 conducted by moving the clamps apart at a speed of 5 in/min (12.7 cm/min) to a 100% extension, a total stretching distance of 1 inch (2.54 cm). The "engineering stress" (force divided by original cross sectional area) at 100% extension was defined as the "green strength", and is shown in Table 1 for 2 testing temperatures, ambient (25 C) and 40 C.
A different portion of 250g each of the calendered samples of Table 1 were additionally mixed with a typical tire innerliner cure package on the lab mill described above. The mill rolls were kept cool by circulating 24 C water through them. The cure ingredients consisted of 3 phr zinc oxide (KadoxTM 930C from Zinc Corporation of America), 0.5 phr sulfur from R.E. Carroll, Inc. and 1.5 phr MBTS (AltaxTM from R.T. Vanderbilt Company, Inc.). The term "phr" (parts per hundred rubber) designates the proportion of the ingredient level per 100 g of the total elastomer or elastomer composition from Table 1. The compounds were then cured in a hot press at 160 C for 18 to 27 minutes at a time equal to 90%
cure time (t90) plus 2 minutes as determined by a curometer test using an ODR 2000E
(Alpha Instruments), operating at 160 C at 3 arc and a standard oscillation rate of 100 cpm, for 60 min.
All the test results are shown in Table 1. Samples 1A through 1D show a progressive increase in green strength with amine levels from zero to 1.5 phr.
This increase in green strength indicates an ionic association between the polymer molecules with addition of the tertiary amine.
For compounds 2B and 3B, green strength at an amine level of 0.5 phr was similar to the green strength of sample 1D at 1.5 phr level of the amine, with sample 3B having a somewhat higher green strength than sample 2B. This indicates that in the presence of EXXPROTM 89-1 Elastomer, the ionic association was much stronger. At 1.0 and 1.5 phr of amine, MB compounds 2 and 3 exhibited very high viscosities such that calendering could not produce smooth sheets.
Cured compound results are shown in terms of hardness in Shore A units.
It is normally experienced that hardness goes up with heat aging in halobutyl corripounds as is the case with compounds 1A, 2A and 3A. However, the addition of tertiary amine reduced the hardening with aging under heat. It can be seen in Table 1 that 0.5 to 1.0 phr of tertiary amine is enough to virtually stop heat aging after 48 hours of exposure at 125 C.
This example demonstrates increased green strength with the addition of tertiary amine to bromobutyl compounds and particularly when brominated poly(isobutylene-co-p-methylstyrene) (EXXPROTM Elastomers) present in the compound. The example also demonstrates improved heat aging stability with the addition of a tertiary amine to bromobutyl and to mixtures of bromobutyl and EXXPROTM Elastomer.
Example 2 A series of compounds shown in Table 2A was mixed in an internal lab mixer following the procedure described in Example 1. Three elastomers were used in this series, the two described in Example 1(bromobutyl 2222 and EXXPROTM 89-1 Elastomer) and a third brominated poly(isobutylene-co p-methylstyrene) elastomer, EXXPROTM 3035 Elastomer (ExxonMobil Chemical Company, Houston TX). The third polymer had a backbone containing 5% by weight PMS before bromination, 0.48 mole% of bromine, and a Mooney viscosity of 45 at 125 C (1+8) (ASTM D1646 modified). In this series, the tertiary amine was introduced into the internal mixer close to the end of the mixing cycle.
The cure package described in Example 1 was also used in this example by incorporating it on a 2-roll rubber mill as described in Example 1.
In this series, pairs of compounds are compared with and without added tertiary amine. Compounds 4A and 4B compare bromobutyl based compounds, 5A and 5B compare compositions of bromobutyl with 2.0 phr of EXXPROTM 89-1 Elastomer, and 6A and 6B compare bromobutyl compositions with 2.0 phr of EXXPROTM 3035 Elastomer. For the straight bromobutyl 1 phr amine was added in compound 4B and for the mixed elastomer compounds a lower level of the same amine, 0.5 phr, was added in compounds 5B and 6B.
The green strength of each compound of Example 2 was tested as in Example 1, but the samples were extended to break at 40 C and an extension rate of 10 in/min (25.4 cm/min). This "example demonstrates an increase of 100%
modulus (a measure of green strength) with the addition of amine. The 6A and pair, where EXXPROTM 3035 Elastomer was used, show the highest increase in 100% modulus and elongation to break. In this example, as in Example 1, addition of amine reduces heat-aging affects. It is shown in Table 2B that all compounds containing the tertiary amine show lesser changes with heat aging for cured modulus, elongation and hardness.
The example also shows that amine addition does not affect the physical properties of the unaged compounds. Further, the improved heat aging stability by adding the tertiary amine is shown for bromobutyl compounds with or without the presence of EXXPROTM Elastomer polymers in the composition.
This increase in green strength indicates an ionic association between the polymer molecules with addition of the tertiary amine.
For compounds 2B and 3B, green strength at an amine level of 0.5 phr was similar to the green strength of sample 1D at 1.5 phr level of the amine, with sample 3B having a somewhat higher green strength than sample 2B. This indicates that in the presence of EXXPROTM 89-1 Elastomer, the ionic association was much stronger. At 1.0 and 1.5 phr of amine, MB compounds 2 and 3 exhibited very high viscosities such that calendering could not produce smooth sheets.
Cured compound results are shown in terms of hardness in Shore A units.
It is normally experienced that hardness goes up with heat aging in halobutyl corripounds as is the case with compounds 1A, 2A and 3A. However, the addition of tertiary amine reduced the hardening with aging under heat. It can be seen in Table 1 that 0.5 to 1.0 phr of tertiary amine is enough to virtually stop heat aging after 48 hours of exposure at 125 C.
This example demonstrates increased green strength with the addition of tertiary amine to bromobutyl compounds and particularly when brominated poly(isobutylene-co-p-methylstyrene) (EXXPROTM Elastomers) present in the compound. The example also demonstrates improved heat aging stability with the addition of a tertiary amine to bromobutyl and to mixtures of bromobutyl and EXXPROTM Elastomer.
Example 2 A series of compounds shown in Table 2A was mixed in an internal lab mixer following the procedure described in Example 1. Three elastomers were used in this series, the two described in Example 1(bromobutyl 2222 and EXXPROTM 89-1 Elastomer) and a third brominated poly(isobutylene-co p-methylstyrene) elastomer, EXXPROTM 3035 Elastomer (ExxonMobil Chemical Company, Houston TX). The third polymer had a backbone containing 5% by weight PMS before bromination, 0.48 mole% of bromine, and a Mooney viscosity of 45 at 125 C (1+8) (ASTM D1646 modified). In this series, the tertiary amine was introduced into the internal mixer close to the end of the mixing cycle.
The cure package described in Example 1 was also used in this example by incorporating it on a 2-roll rubber mill as described in Example 1.
In this series, pairs of compounds are compared with and without added tertiary amine. Compounds 4A and 4B compare bromobutyl based compounds, 5A and 5B compare compositions of bromobutyl with 2.0 phr of EXXPROTM 89-1 Elastomer, and 6A and 6B compare bromobutyl compositions with 2.0 phr of EXXPROTM 3035 Elastomer. For the straight bromobutyl 1 phr amine was added in compound 4B and for the mixed elastomer compounds a lower level of the same amine, 0.5 phr, was added in compounds 5B and 6B.
The green strength of each compound of Example 2 was tested as in Example 1, but the samples were extended to break at 40 C and an extension rate of 10 in/min (25.4 cm/min). This "example demonstrates an increase of 100%
modulus (a measure of green strength) with the addition of amine. The 6A and pair, where EXXPROTM 3035 Elastomer was used, show the highest increase in 100% modulus and elongation to break. In this example, as in Example 1, addition of amine reduces heat-aging affects. It is shown in Table 2B that all compounds containing the tertiary amine show lesser changes with heat aging for cured modulus, elongation and hardness.
The example also shows that amine addition does not affect the physical properties of the unaged compounds. Further, the improved heat aging stability by adding the tertiary amine is shown for bromobutyl compounds with or without the presence of EXXPROTM Elastomer polymers in the composition.
Example 3 A series of tire innerliner model compounds shown in Table 3 was mixed in an internal lab mixer following the procedure of Example 2, where all ingredients were added to the internal mixer. The series is based on a composition of 70/30 brominated-star-branched butyl (BrSBB 6222, ExxonMobil Chemical Company, Houston TX) with a brominated poly(isobutylene-cop-methylstyrene) (EXXPROTM 90-3 Elastomer, ExxonMobil Chemical). The BrSBB 6222 contained a specified amount of 2.4 % by weight bromine and had a Mooney viscosity of 32 at 125 C (1+8) (ASTM D1646 modified). The EXXPROTM
Elastomer, 90-3, had a backbone containing 5 wt% of PMS before bromination and had 0.52 mole% bromine and a Mooney viscosity of 55 at 125 C. In the compounds of this series, a homogenizing agent, Struktol 40 MS (StruktolTM
Company) and a tackifying phenolic resin, SP-1068 (Schenectady International Inc.) were also used. The tertiary amine of this series was trihexadecylamine from the same source as the amine of Examples 1 and 2.
The compounds of this series contain an increasing amount of amine from zero in compound 7 to 1.08 phr in compound 10. Green tensile strength was tested for the compounds of Table 3 following the procedure used in Example 2, at 40 C. The 100% modulus and elongation to break of all the compounds in Table 3 are not significantly different from each other. This example demonstrates that a tertiary amine which is highly hindered such as trihexadecyl amine, having 3 C16 branches attached to the nitrogen, is not effective in creating strong associations between the polymer chains as the amine of Examples 1 and 2.
In all, these examples show the utility of the present invention. By addition of a tertiary amine to the rubber and copolymer components the green strength is increased, while also improving the thermal stability of the cured product. The data in Tables 1 and 2 shown that; in the case of Bromobuty12222 alone, the presence of amine improves thermal stability. When a halogenated isoolefin/alkylstyrene such as an EXXPROTM Elastomer is present with the Bromobutyl 2222, and amine is then added, the green strength and thermal stability is improved. The amounts of the various components can be modified to suit different manufacturing needs, as well as the choice of the amine itself.
While the present invention has been described and illustrated by reference to particular embodiments, those of ordinary skill in the art will appreciate that the invention lends itself to many different variations not illustrated herein. For these reasons, then, reference should be made solely to the appended claims for purposes of determining the true scope of the present invention.
r. o OON o o O o N O O M N wi O C
O CF' l~ Vl M
M O O O O N 'n O N ~ VM'~
O O
M ~F M =--~
o O O o N O O M N ~N cn O O
kf) O O O o N l-O o N O ~--! O
N o0 O
M A O O M
M M
Qi~ O O W) kn rl h O tn c.~ vi v .-I
t~. V o 0 0 o i M N cV Ki Vi W~
~
kn N M N h O O
ri ^~ o N 01 E o N
N
E ccl cct 4 00 U o p 4 0 v b aQi ' ,~ C7 U c on cn 1. ~r ~D
p N o o ~W?
Q O
O p O O O N tn 00 N --~ Vl O0 N O o O N,.~..i V?
~ O p cl' p o N o o U~ 0 N~ p =i QI
O o ~
kn N o 0 0 o N^ ~
y o r.
E'+
o 0 0 ON~o n~ N ~ M a~
C,' N c C
p O
O O
cti cn "0 0 ~ '0 ~ bAZ ~
a"a wwwa v~
M pp 01 00 00 t- 01 --~ .--i N ~ N 'd= 'a; 01 '~; 01 ,~ ~i' M\G 00 ~O M N
N V00 oo ~oo l-Vl kn kn V1 N N
kn kn 00 ~~j ~1 00 +n ~ p ~n ~O ~ =--~ ~O .-+ ~O kn in vn rõ F F
o w ~ a~i a~i ,h N V "O 00 U~ N V l~ ,~ l~
V] N y~ F N l, - = oo Oi ~ kn 6) p M .--i \O .-.~ k!1 l() W) rA
G F 11 rh cq V'1 b~A --~ ~=
N 00 00 kn ~+ Pa tw v? ~t a~
y U M y =--~ \O .-~ ~O .--i ~ 0 vM'~ v~i O V1 u of ~
Qn U) 00 4) oo n F oo ~
y r~ N 00 =y ~ "o 06 0 '..i c1' o M ~-i \O ,I"'=i .-~ N Vl F F
co `d - 0-cn ~ ~ N dO=
4 ~
O~ O ~.J O=~ O=5 bp 00 cd S cd ~F 7 C1~
\ W \ \ \ ~
O O \ O ~
O\ Q Q
~ ~ ~
Table 3. Compositions 7-10 Compound (phr) 7 8 9 10 rSBB 6222 70 70 70 70 EXXPROTM 90-3 Elastomer 30 30 30 30 araffinic Oil 10 10 10 10 Strukto140 MS 5 5 5 5 660 Black 60 60 60 60 SP-1068 Resin 4 4 4 4 Stearic Acid 2 2 2 2 MgO 0.15 0.15 0.15 0.15 rihexadecylamine 0 0.36 0.72 1.08 Green Tensile Strength, 40 C
100%Modulus, MPa 0.239 0.237 0.235 0.256 % 1Elongation 376 374 426 365
Elastomer, 90-3, had a backbone containing 5 wt% of PMS before bromination and had 0.52 mole% bromine and a Mooney viscosity of 55 at 125 C. In the compounds of this series, a homogenizing agent, Struktol 40 MS (StruktolTM
Company) and a tackifying phenolic resin, SP-1068 (Schenectady International Inc.) were also used. The tertiary amine of this series was trihexadecylamine from the same source as the amine of Examples 1 and 2.
The compounds of this series contain an increasing amount of amine from zero in compound 7 to 1.08 phr in compound 10. Green tensile strength was tested for the compounds of Table 3 following the procedure used in Example 2, at 40 C. The 100% modulus and elongation to break of all the compounds in Table 3 are not significantly different from each other. This example demonstrates that a tertiary amine which is highly hindered such as trihexadecyl amine, having 3 C16 branches attached to the nitrogen, is not effective in creating strong associations between the polymer chains as the amine of Examples 1 and 2.
In all, these examples show the utility of the present invention. By addition of a tertiary amine to the rubber and copolymer components the green strength is increased, while also improving the thermal stability of the cured product. The data in Tables 1 and 2 shown that; in the case of Bromobuty12222 alone, the presence of amine improves thermal stability. When a halogenated isoolefin/alkylstyrene such as an EXXPROTM Elastomer is present with the Bromobutyl 2222, and amine is then added, the green strength and thermal stability is improved. The amounts of the various components can be modified to suit different manufacturing needs, as well as the choice of the amine itself.
While the present invention has been described and illustrated by reference to particular embodiments, those of ordinary skill in the art will appreciate that the invention lends itself to many different variations not illustrated herein. For these reasons, then, reference should be made solely to the appended claims for purposes of determining the true scope of the present invention.
r. o OON o o O o N O O M N wi O C
O CF' l~ Vl M
M O O O O N 'n O N ~ VM'~
O O
M ~F M =--~
o O O o N O O M N ~N cn O O
kf) O O O o N l-O o N O ~--! O
N o0 O
M A O O M
M M
Qi~ O O W) kn rl h O tn c.~ vi v .-I
t~. V o 0 0 o i M N cV Ki Vi W~
~
kn N M N h O O
ri ^~ o N 01 E o N
N
E ccl cct 4 00 U o p 4 0 v b aQi ' ,~ C7 U c on cn 1. ~r ~D
p N o o ~W?
Q O
O p O O O N tn 00 N --~ Vl O0 N O o O N,.~..i V?
~ O p cl' p o N o o U~ 0 N~ p =i QI
O o ~
kn N o 0 0 o N^ ~
y o r.
E'+
o 0 0 ON~o n~ N ~ M a~
C,' N c C
p O
O O
cti cn "0 0 ~ '0 ~ bAZ ~
a"a wwwa v~
M pp 01 00 00 t- 01 --~ .--i N ~ N 'd= 'a; 01 '~; 01 ,~ ~i' M\G 00 ~O M N
N V00 oo ~oo l-Vl kn kn V1 N N
kn kn 00 ~~j ~1 00 +n ~ p ~n ~O ~ =--~ ~O .-+ ~O kn in vn rõ F F
o w ~ a~i a~i ,h N V "O 00 U~ N V l~ ,~ l~
V] N y~ F N l, - = oo Oi ~ kn 6) p M .--i \O .-.~ k!1 l() W) rA
G F 11 rh cq V'1 b~A --~ ~=
N 00 00 kn ~+ Pa tw v? ~t a~
y U M y =--~ \O .-~ ~O .--i ~ 0 vM'~ v~i O V1 u of ~
Qn U) 00 4) oo n F oo ~
y r~ N 00 =y ~ "o 06 0 '..i c1' o M ~-i \O ,I"'=i .-~ N Vl F F
co `d - 0-cn ~ ~ N dO=
4 ~
O~ O ~.J O=~ O=5 bp 00 cd S cd ~F 7 C1~
\ W \ \ \ ~
O O \ O ~
O\ Q Q
~ ~ ~
Table 3. Compositions 7-10 Compound (phr) 7 8 9 10 rSBB 6222 70 70 70 70 EXXPROTM 90-3 Elastomer 30 30 30 30 araffinic Oil 10 10 10 10 Strukto140 MS 5 5 5 5 660 Black 60 60 60 60 SP-1068 Resin 4 4 4 4 Stearic Acid 2 2 2 2 MgO 0.15 0.15 0.15 0.15 rihexadecylamine 0 0.36 0.72 1.08 Green Tensile Strength, 40 C
100%Modulus, MPa 0.239 0.237 0.235 0.256 % 1Elongation 376 374 426 365
Claims (71)
1. A composition comprising:
at least one isoolefin copolymer comprising a halomethylstyrene derived unit, the isoolefin having between 4 and 7 carbon atoms and the copolymer containing from 0.5%
to 20% by weight halomethylstyrene; and an amine compound represented by the formula (R1R2R3)N, wherein R1 is either hydrogen or a C4 to C30 hydrocarbyl group, R2 is either hydrogen or a C1 to hydrocarbyl group; and R3 is either hydrogen or a C1 to C30 hydrocarbyl group, provided that at least one of R1, R2 and R3 is not hydrogen.
at least one isoolefin copolymer comprising a halomethylstyrene derived unit, the isoolefin having between 4 and 7 carbon atoms and the copolymer containing from 0.5%
to 20% by weight halomethylstyrene; and an amine compound represented by the formula (R1R2R3)N, wherein R1 is either hydrogen or a C4 to C30 hydrocarbyl group, R2 is either hydrogen or a C1 to hydrocarbyl group; and R3 is either hydrogen or a C1 to C30 hydrocarbyl group, provided that at least one of R1, R2 and R3 is not hydrogen.
2. The composition of claim 1, wherein the composition also comprises an additional rubber component which is butyl rubber, halogenated butyl rubber, star-branched butyl rubber, halogenated star-branched butyl rubber, isobutylene homopolymer, butadiene rubber, neoprene, nitrile rubbers, ethylene/propylene/diene terpolymers, ethylene/propylene copolymers, styrene butadiene rubbers, polybutadiene, polyisoprene, isoolefin/alkylstyrene copolymer, halogenated isoolefin/alkylstyrene copolymer natural rubber, polypropylene, polyethylene, polyurethane, polyvinyl chloride, silicon rubber, propylene oxide polymer, or a mixture thereof.
3. The composition of claim 2, wherein the rubber component is present in the composition from 5% to 95% by weight of the composition.
4. The composition of claim 1, wherein the rubber component is halogenated butyl rubber.
5. The composition of claim 1, wherein the isoolefin copolymer is a halogenated poly(isobutylene-co-p-methylstyrene).
6. The composition of claim 5, wherein from 0.01 mole % to 60 mole % of the methyl groups present on the styrene are halomethyl groups.
7. The composition of claim 4, wherein the halogenated butyl rubber contains from 85% to 99.5% by weight repeat units derived from isobutylene, from 0.1 to 15%
by weight repeat units derived from conjugated diene and from 0.1% to 15% by weight halogen.
by weight repeat units derived from conjugated diene and from 0.1% to 15% by weight halogen.
8. The composition of claim 4, wherein the halogenated butyl rubber contains from 85% to 99.5% by weight repeat units derived from isobutylene, from 0.1 to 15%
by weight repeat units derived from isoprene and from 0.1% to 15% by weight bromine.
by weight repeat units derived from isoprene and from 0.1% to 15% by weight bromine.
9. The composition of claim 5, wherein the copolymer contains isobutylene from 88% to 98% by weight copolymer.
10. The composition of claim 1, wherein the composition contains from 0.05 to 2 mole equivalents of amine relative to the number of moles of halogen present in the composition.
11. The composition of claim 1, wherein R3 is a C1 to C8 hydrocarbyl group.
12. The composition of claim 1, wherein both R1 and R2 are hydrogen.
13. The composition of claim 1, wherein both R1 and R2 are C4 to C30 hydrocarbyl groups.
14. The composition of claim 1, wherein R1 is a C4 to C30 hydrocarbyl group and R2 is a C1 to C4 hydrocarbyl group.
15. The composition of claim 1, wherein R1 is a C4 to C30 hydrocarbyl group, R2 is a C1 to C4 hydrocarbyl group and R3 is a C1 to C8 hydrocarbyl group.
16. The composition of claim 1, wherein the amine compound is N,N-dimethylhexadecylamine, N,N-dimethylhexylamine, N,N-dimethyldodecylamine, N,N-dimethyloctadecylamine, N,N-diethyldecylamine, N,N-dimethylbenzylamine, N,N-methylpropylhexadecylamine, or morpholine.
17. The composition of claim 1, wherein the amine is present from 0.01 to 5 wt% of the composition.
18. The composition of claim 1, wherein the composition is cured.
19. A composition comprising:
from 5% to 95% by weight of a rubber component;
an amine compound represented by the formula (R1R2R3)N, wherein R1 is either hydrogen or a C4 to C30 hydrocarbyl group, R2 is either hydrogen or a C1 to hydrocarbyl group; and R3 is either hydrogen or a C1 to C30 hydrocarbyl group, provided that at least one of R1, R2 and R3 is not hydrogen; and at least one isoolefin copolymer comprising a halomethylstyrene derived unit, the isoolefin having between 4 and 7 carbon atoms and the copolymer containing from 0.5%
to 20% by weight halomethylstyrene, the isoolefin having between 4 and 7 carbon atoms.
from 5% to 95% by weight of a rubber component;
an amine compound represented by the formula (R1R2R3)N, wherein R1 is either hydrogen or a C4 to C30 hydrocarbyl group, R2 is either hydrogen or a C1 to hydrocarbyl group; and R3 is either hydrogen or a C1 to C30 hydrocarbyl group, provided that at least one of R1, R2 and R3 is not hydrogen; and at least one isoolefin copolymer comprising a halomethylstyrene derived unit, the isoolefin having between 4 and 7 carbon atoms and the copolymer containing from 0.5%
to 20% by weight halomethylstyrene, the isoolefin having between 4 and 7 carbon atoms.
20. The composition of claim 19, wherein the rubber component is butyl rubber, halogenated butyl rubber, star-branched butyl rubber, halogenated star-branched butyl rubber, isobutylene homopolymer, butadiene rubber, neoprene, nitrile rubbers, ethylene/propylene/diene terpolymers, ethylene/propylene copolymers, styrene butadiene rubbers, polybutadiene, polyisoprene, isoolefin/alkylstyrene copolymer, halogenated isoolefin/alkylstyrene copolymer, natural rubber, polypropylene, polyethylene, polyurethane, polyvinyl chloride, silicon rubber, propylene oxide polymer, or a mixture thereof.
21. The composition of claim 19, wherein the rubber component is halogenated butyl rubber.
22. The composition of claim 19, wherein the rubber component is a halogenated isoolefin/alkylstyrene copolymer.
23. The composition of claim 21, wherein the halogenated butyl rubber contains from 85% to 99.5% by weight repeat units derived from isobutylene, from 0.1 to 15%
by weight repeat units derived from conjugated diene and from 0.1% to 15% by weight halogen.
by weight repeat units derived from conjugated diene and from 0.1% to 15% by weight halogen.
24. The composition of claim 22, wherein the copolymer contains isobutylene from 88% to 98% by weight of the copolymer.
25. The composition of claim 19, wherein the isoolefin copolymer is halogenated poly(isobutylene-co-p-methylstyrene).
26. The composition of claim 25, wherein from 0.01 mole % to 60 mole % of the methyl groups are halomethyl groups.
27. The composition of claim 19, wherein the composition contains from 0.05 to mole equivalents of amine relative to the number of moles of halogen present in the composition.
28. The composition of claim 19, wherein R3 is a C1 to C8 hydrocarbyl group.
29. The composition of claim 19, wherein both R1 and R2 are hydrogen.
30. The composition of claim 19, wherein both R1 and R2 are C4 to C30 hydrocarbyl groups.
31. The composition of claim 19, wherein R1 is a C4 to C30 hydrocarbyl group and R2 is a C1 to C4 hydrocarbyl group.
32. The composition of claim 19, wherein R1 is a C4 to C30 hydrocarbyl group, R2 is a C1 to C4 hydrocarbyl group and R3 is a C1 to C8 hydrocarbyl group.
33. The composition of claim 19, wherein the amine compound is N,N-dimethylhexadecylamine, N,N-dimethylhexylamine, N,N-dimethyldodecylamine, N,N-dimethyloctadecylamine, N,N-diethyldecylamine, N,N-dimethylbenzylamine, N,N-methylpropylhexadecylamine, or a morpholine.
34. The composition of claim 19, wherein the amine compound is N,N-dimethyl hexadecylamine.
35. The composition of claim 19, wherein the composition is cured.
36. A method of forming a composition comprising combining:
an amine and a isoolefin copolymer comprising halomethylstyrene moieties present from 95% to 5% by weight of the composition, and wherein the isoolefin having between 4 and 7 carbon atoms and the copolymer containing from 0.5% to 20% by weight halomethylstyrene; and wherein the amine compound represented by the formula (R1R2R3)N, wherein R1 is either hydrogen or a C4 to C30 hydrocarbyl group, R2 is either hydrogen or a C1 to C30 hydrocarbyl group; and R3 is either hydrogen or a C1 to C30 hydrocarbyl group, provided that at least one of R1, R2 and R3 is not hydrogen.
an amine and a isoolefin copolymer comprising halomethylstyrene moieties present from 95% to 5% by weight of the composition, and wherein the isoolefin having between 4 and 7 carbon atoms and the copolymer containing from 0.5% to 20% by weight halomethylstyrene; and wherein the amine compound represented by the formula (R1R2R3)N, wherein R1 is either hydrogen or a C4 to C30 hydrocarbyl group, R2 is either hydrogen or a C1 to C30 hydrocarbyl group; and R3 is either hydrogen or a C1 to C30 hydrocarbyl group, provided that at least one of R1, R2 and R3 is not hydrogen.
37. The method of claim 36, further comprising combining an additional rubber component, wherein the additional rubber component is a butyl rubber, halogenated butyl rubber, star-branched butyl rubber, halogenated star-branched butyl rubber, isobutylene homopolymer, butadiene rubber, neoprene, nitrile, rubbers, ethylene/propylene/diene terpolymer, ethylene/propylene copolymer, styrene butadiene rubber, polybutadiene, polyisoprene, isoolefin/alkylstyrene copolymer, halogenated isoolefin/alkylstyrene copolymer, natural rubber, polypropylene, polyethylene, polyurethane, polyvinyl chloride, silicon rubber, propylene oxide polymer, or a mixture thereof.
38. The method of claim 37, wherein the additional rubber component is present from 5% to 95% by weight of the composition.
39. The method of claim 37, wherein the additional rubber component is halogenated butyl rubber.
40. The method of claim 39, wherein the halogenated butyl rubber contains from 85%
to 99.5% by weight repeat units derived from isobutylene, from 0.1 to 15% by weight repeat units derived from conjugated diene and from 0.1% to 15% by weight halogen.
to 99.5% by weight repeat units derived from isobutylene, from 0.1 to 15% by weight repeat units derived from conjugated diene and from 0.1% to 15% by weight halogen.
41. The method of claim 39, wherein the halogenated butyl rubber contains from 85%
to 99.5% by weight repeat units derived from isobutylene, from 0.1 to 15% by weight repeat units derived from isoprene and from 0.1 % to 15% by weight bromine.
to 99.5% by weight repeat units derived from isobutylene, from 0.1 to 15% by weight repeat units derived from isoprene and from 0.1 % to 15% by weight bromine.
42. The method of claim 36, wherein the copolymer contains isobutylene from 88% to 98% by weight copolymer.
43. The method of claim 36, wherein the copolymer is halogenated poly(isobutylene-co-p-methylstyrene).
44. The method of claim 43, wherein from 0.01 mole % to 60 mole % of the methyl groups are halomethyl groups.
45. The method of claim 36, wherein the composition contains from 0.05 to 2 mole equivalents of amine relative to the number of moles of halogen present in the composition.
46. The method of claim 36, wherein R3 is a C1 to C8 hydrocarbyl group.
47. The method of claim 36, wherein both R1 and R2 are hydrogen.
48. The method of claim 36, wherein both R1 and R2 are C4 to C30 hydrocarbyl groups.
49. The method of claim 36, wherein R1 is a C4 to C30 hydrocarbyl group and R2 is a C1 to C4 hydrocarbyl group.
50. The method of claim 36, wherein R1 is a C4 to C30 hydrocarbyl group and R
2 is a C1 to C4 hydrocarbyl group and R3 is a C1 to C8 hydrocarbyl group.
2 is a C1 to C4 hydrocarbyl group and R3 is a C1 to C8 hydrocarbyl group.
51. The method of claim 36, wherein the amine compound is N,N-dimethylhexadecylamine, N,N-dimethylhexylamine, N,N-dimethyldodecylamine, N,N-dimethyloctadecylamine, N,N-diethyldecylamine, N,N-dimethylbenzylamine, N,N-methylpropylhexadecylamine, or morpholine.
52. The composition of claim 36, wherein the amine is present from 0.01 to 5 wt% of the composition.
53. The method of claim 36, wherein the composition is cured.
54. A method of forming a composition comprising combining:
from 5% to 95% by weight of a rubber component;
an amine compound represented by the formula (R1R2R3)N, wherein R1 is either hydrogen or a C4 to C30 hydrocarbyl group, R2 is either hydrogen or a C1 to hydrocarbyl group; and R3 is either hydrogen or a C1 to C30 hydrocarbyl group, provided that at least one of R1, R2 and R3 is not hydrogen; and a isoolefin copolymer comprising a halomethylstyrene derived unit from 95% to 5% by weight of the composition, the isoolein having between 4 and 7 carbon atoms and the copolymer containing from 0.5% to 20% by weight halomethylstyrene.
from 5% to 95% by weight of a rubber component;
an amine compound represented by the formula (R1R2R3)N, wherein R1 is either hydrogen or a C4 to C30 hydrocarbyl group, R2 is either hydrogen or a C1 to hydrocarbyl group; and R3 is either hydrogen or a C1 to C30 hydrocarbyl group, provided that at least one of R1, R2 and R3 is not hydrogen; and a isoolefin copolymer comprising a halomethylstyrene derived unit from 95% to 5% by weight of the composition, the isoolein having between 4 and 7 carbon atoms and the copolymer containing from 0.5% to 20% by weight halomethylstyrene.
55. The method of claim 54, wherein the rubber component is butyl rubber, halogenated butyl rubber, star-branched butyl rubber, halogenated star-branched butyl rubber, isobutylene homopolymer, butadiene rubber, neoprene, nitrile rubbers, ethylene/propylene/diene terpolymer, ethylene/propylene copolymer, styrene butadiene rubber, polybutadiene, polyisoprene, isoolefin/alkylstyrene copolymer, halogenated isoolefin/alkylstyrene copolymer, natural rubber, polypropylene, polyethylene, polyurethane, polyvinyl chloride, silicon rubber, propylene oxide polymer, or a mixture thereof.
56. The method of claim 54, wherein the rubber component is halogenated butyl rubber.
57. The method of claim 56, wherein the halogenated butyl rubber contains from 85%
to 99.5% by weight repeat units derived from isobutylene, from 0.1 to 15% by weight repeat units derived from conjugated diene and from 0.1% to 15 % by weight halogen.
to 99.5% by weight repeat units derived from isobutylene, from 0.1 to 15% by weight repeat units derived from conjugated diene and from 0.1% to 15 % by weight halogen.
58. The method of claim 56, wherein the halogenated butyl rubber contains from 85%
to 99.5% by weight repeat units derived from isobutylene, from 0.1 to 15% by weight repeat units derived from isoprene and from 0.1% to 15% by weight bromine.
to 99.5% by weight repeat units derived from isobutylene, from 0.1 to 15% by weight repeat units derived from isoprene and from 0.1% to 15% by weight bromine.
59. The method of claim 54, wherein the copolymer contains isobutylene from 88% to 98% by weight copolymer.
60. The method of claim 54, wherein the copolymer is halogenated poly(isobutylene-co-p-methylstyrene).
61. The method of claim 60, wherein from 0.01 mole % to 60 mole % of the methyl groups present on the benzene ring of the alkylstyrene contain a halogen atom.
62. The method of claim 54, wherein the composition contains from 0.05 to 2 mole equivalents of amine relative to the number of moles of halogen present in the composition.
63. The method of claim 54, wherein R3 is a C1 to C8 hydrocarbyl group.
64. The method of claim 54, wherein both R1 and R2 are C4 to C30 are hydrogen.
65. The method of claim 54, wherein both R1 and R2 are C4 to C30 hydrocarbyl groups.
66. The method of claim 54, wherein R1 is a C4 to C30 hydrocarbyl group and R2 is a C1 to C4 hydrocarbyl group.
67. The method of claim 54, wherein R1 is a C4 to C30 hydrocarbyl group, R2 is a C1 to C4 hydrocarbyl group and R3 is a C1 to C8 hydrocarbyl group.
68. The method of claim 54, wherein the amine compound is N,N-dimethylhexadecylamine, N,N-dimethylhexylamine, N,N-dimethyldodecylamine, N,N-dimethyloctadecylamine, N,N-diethyldecylamine, N,N-dimethylbenzylamine, N,N-methylpropylhexadecylamine, or morpholine.
69. The method of claim 54, wherein the amine compound is N,N-dimethylhexadecylamine.
70. The method of claim 54, wherein the amine is present from 0.01 to 5 wt% of the composition.
71. The method of claim 1, wherein the composition is cured.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US09/686,215 | 2000-10-11 | ||
| US09/686,215 US6552108B1 (en) | 2000-10-11 | 2000-10-11 | Rubber blends having improved stability and green strength |
| PCT/US2001/031431 WO2002031039A1 (en) | 2000-10-11 | 2001-10-09 | Halogenated elastomeric compositions having improved stability and green strength |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2423206A1 CA2423206A1 (en) | 2002-04-18 |
| CA2423206C true CA2423206C (en) | 2009-12-15 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002423206A Expired - Fee Related CA2423206C (en) | 2000-10-11 | 2001-10-09 | Halogenated elastomeric compositions having improved stability and green strength |
Country Status (16)
| Country | Link |
|---|---|
| US (2) | US6552108B1 (en) |
| EP (1) | EP1353989B1 (en) |
| JP (1) | JP4059765B2 (en) |
| KR (1) | KR20040005835A (en) |
| CN (1) | CN1247678C (en) |
| AT (1) | ATE442412T1 (en) |
| AU (1) | AU2001296712A1 (en) |
| BR (1) | BR0114409A (en) |
| CA (1) | CA2423206C (en) |
| CZ (1) | CZ20031000A3 (en) |
| DE (1) | DE60139901D1 (en) |
| HU (1) | HUP0302689A2 (en) |
| MX (1) | MXPA03003194A (en) |
| PL (1) | PL365611A1 (en) |
| RU (1) | RU2320687C2 (en) |
| WO (1) | WO2002031039A1 (en) |
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-
2000
- 2000-10-11 US US09/686,215 patent/US6552108B1/en not_active Expired - Fee Related
-
2001
- 2001-10-09 MX MXPA03003194A patent/MXPA03003194A/en not_active Application Discontinuation
- 2001-10-09 DE DE60139901T patent/DE60139901D1/en not_active Expired - Lifetime
- 2001-10-09 HU HU0302689A patent/HUP0302689A2/en unknown
- 2001-10-09 AT AT01977606T patent/ATE442412T1/en not_active IP Right Cessation
- 2001-10-09 KR KR10-2003-7005136A patent/KR20040005835A/en not_active Application Discontinuation
- 2001-10-09 PL PL01365611A patent/PL365611A1/en not_active Application Discontinuation
- 2001-10-09 RU RU2003110956/04A patent/RU2320687C2/en not_active IP Right Cessation
- 2001-10-09 WO PCT/US2001/031431 patent/WO2002031039A1/en active Application Filing
- 2001-10-09 CA CA002423206A patent/CA2423206C/en not_active Expired - Fee Related
- 2001-10-09 EP EP01977606A patent/EP1353989B1/en not_active Expired - Lifetime
- 2001-10-09 AU AU2001296712A patent/AU2001296712A1/en not_active Abandoned
- 2001-10-09 US US10/398,302 patent/US6956075B2/en not_active Expired - Fee Related
- 2001-10-09 BR BR0114409-0A patent/BR0114409A/en not_active IP Right Cessation
- 2001-10-09 CN CNB018171923A patent/CN1247678C/en not_active Expired - Fee Related
- 2001-10-09 JP JP2002534415A patent/JP4059765B2/en not_active Expired - Fee Related
- 2001-10-09 CZ CZ20031000A patent/CZ20031000A3/en unknown
Also Published As
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| JP2004514744A (en) | 2004-05-20 |
| CN1247678C (en) | 2006-03-29 |
| AU2001296712A1 (en) | 2002-04-22 |
| US6956075B2 (en) | 2005-10-18 |
| CN1469897A (en) | 2004-01-21 |
| DE60139901D1 (en) | 2009-10-22 |
| ATE442412T1 (en) | 2009-09-15 |
| PL365611A1 (en) | 2005-01-10 |
| RU2003110956A (en) | 2005-01-27 |
| HUP0302689A2 (en) | 2003-11-28 |
| US6552108B1 (en) | 2003-04-22 |
| WO2002031039A1 (en) | 2002-04-18 |
| US20040097654A1 (en) | 2004-05-20 |
| JP4059765B2 (en) | 2008-03-12 |
| EP1353989A4 (en) | 2004-05-26 |
| CA2423206A1 (en) | 2002-04-18 |
| EP1353989B1 (en) | 2009-09-09 |
| RU2320687C2 (en) | 2008-03-27 |
| KR20040005835A (en) | 2004-01-16 |
| BR0114409A (en) | 2003-12-30 |
| CZ20031000A3 (en) | 2003-11-12 |
| EP1353989A1 (en) | 2003-10-22 |
| MXPA03003194A (en) | 2004-05-21 |
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